Slime control compositions and their use

ABSTRACT

The present invention relates to certain processes and compositions useful for inhibiting the growth of slime in water and, in particular, water used for industrial purposes; for example, in the manufacture of pulp paper, in the manufacture of paper, in cooling water systems and in effluent water treatment. The novel processes and compositions of the present invention are processes or mixtures which show unexpected synergistic activity against microorganisms, including bacteria, fungi and algae, which produce slime in aqueous systems or bodies which are objectionable from either an operational or aesthetic point of view. Specifically, the invention is directed to the use of compositions comprising a combination of a bromonitrostyrene and cetyl trimethyl ammonium p-toluene sulfonate.

United States Patent 11 1 Shema et al.

[ SLIME CONTROL COMPOSITIONS AND THEIR USE [75 Inventors: Bernard F. Shema, Glenside; Robert H. Brink, Jr., Doylestown; Paul Swered, Philadelphia, all of Pa.

[73] Assignee: Betz Laboratories, Inc., Trevose, Pa.

[22] Filed: Apr. 9, 1973 [21] Appl. No.: 349,358

Related U.S. Application Data [63] Continuationinpart of Ser. No. 271,459, July 13, 1972, Pat. No. 3,827,873, which is a continuation-in-part of Ser. No. 464, Jan. 2, 1970,

abandoned.

[52] U.S. Cl. 424/329; 71/67; 162/161; 424/349 [51] Int. Cl. A01N 9/12;A01N 9/20 [58] Field of Search 424/349, 329

[56] References Cited UNITED STATES PATENTS 2,335,384 11/1943 Bosquet et al. 424/349 3.231.509 1/1966 Shema 424/300 OTHER PUBLlCATlONS Chemical Abstracts 51:8198i (1957).

[451 July 22,1975

Chemical Abstracts 61:1 1051f (1964).

Chemical Asbstracts 70:67163u (1969).

Primary ExaminerA1bert T. Meyers Assistant Examiner-Leonard Schenkman Attorney, Agent, or Firm-Alexander D. Ricci 5 7 ABSTRACT The present invention relates to certain processes and compositions useful for inhibiting the growth of slime in water and, in particular, water used for industrial purposes; for example, in the manufacture of pulp paper, in the manufacture of paper, in cooling water systems and in effluent water treatment. The novel processes and compositions of the present invention are processes or mixtures which show unexpected synergistic activity against microorganisms, including bacteria, fungi and algae, which produce slime in aqueous systems or bodies which are objectionable from either an operational or aesthetic point of view. Specifically, the invention is directed to the use of compositions comprising a combination of a bromonitrostyrene and cetyl trimethyl ammonium p-toluene sulfonate.

8 Claims, N0 Drawings SLIME CONTROL COMPOSITIONS AND THEIR USE This application is a continuation-in-part of application Ser. No. 271,459, filed July 13, 1972, now US. Pat. No. 3,827,873, which in turn is a continuation-inpart of application Ser. No. 464, filed Jan, 2, 1970, now abandoned.

BACKGROUND OF THE INVENTION The formation of slime by microorganisms is a problem which attends many systems. For example, lagoons, lakes, ponds, pools, and such systems as cooling water systems and pulp and paper mill systems all possess conditions which are conducive to the growth and reproduction of slime-forming microorganisms. In both once-through and recirculating cooling systems, for example, which employ large quantities of water as a cooling medium, the formation fo slime by microorganisms is an extensive and constant problem.

Airborne organisms are readily entrained in the water from cooling towers and find this warm medium an ideal environment for growth and multiplication. Aerobic and heliotropic organisms flourish on the tower proper while other organisms colonize and grow in such areas as the tower sump and the piping and passages of the cooling system. Such slime serves to deteriorate the tower structure in the case of wooden towers. In addition, the deposition of slime on metal surfaces promotes corrosion. Furthermore, slime carried through the cooling system plugs and fouls lines, valves, strainers, etc. and deposits on heat exchange surfaces. In the latter case, the impedance of heat transfer can greatly reduce the efficiency of the cooling system.

In pulp and paper mill systems, slime formed by microorganisms isalso frequently and, in fact, commonly encountered. Fouling or plugging by slime also occurs in the case of pulp and paper mill systems. Of greater significance, the slime becomes entrained in the paper produced to cause breakouts on the paper machines with consequent work stoppages and the loss of production time or unsightly blemishes in the final product which results in rejects and wasted output. The previously discussed problems have resulted in the extensive utilization of biocides in cooling water and pulp and paper mill systems. Materials which have enjoyed widespread use in such applications include chlorine, organo-mercurials, chlorinated phenols, organobromines, and various organo-sulfur compounds. All of these compounds are generally useful for this purpose but each is attended by a variety of impediments. For example, chlorination is limited both by its specific toxicity for slime-forming organisms at economic levels and by the ability of chlorine to react which results in the expenditure of the chlorine before its full biocidal function may be achieved. Other biocides are attended by odor problems and hazards in respect to storage, use or handling which limit their utility. To date, no one compound or type of compound has achieved a clearly established predominance in respect to the applications discussed. Likewise, lagoons, ponds, lakes and even pools, either used for pleasure purposes or used for industrial purposes for the disposal and storage of industrial wastes, become, during the warm weather, besieged by slime due to microorganism growth and reproduction. In the case of the recreational areas, the problem of infection, etc. is obvious. In the case of industrial storage or disposal of industrial materials, the

microorganisms cause additional problems which must be eliminated prior to the materials use or the waste is treated for disposal.

Naturally, economy is a major consideration in respect to all of these biocides. Such economic considerations attach to both the cost of the biocide and the expense of its application. The cost-performance index of any biocide is derived from the basic cost of the material, its effectiveness per unit of weight, the duration of its biocidal or biostatic effect in the system treated, and the ease and frequency of its addition to the system treated. To date, none of the commercially availabe biocides have exhibited a prolonged biocidal effect. Instead, their effectiveness is rapidly reduced as the result of exposure to physical conditions such as temperature association with ingredients contained by the system toward which they exhibit an affinity or substantivity, etc., with a resultant restriction or elimination of their biocidal effectiveness.

As a consequence, the use of such biocides involves their continuous or frequent addition to systems to be treated and their addition to a plurality of points or zones in the systems to be treated. Accordingly, the cost of the biocide and the labor cost of such means of applying it are considerable. In other instances, the difficulty of access to the zone in which slime formation is experienced precludes the effective use of a biocide. For example, in a particular system there is no access to an area at which slime formation occurs and it may only be applied at a point which is upstream in the flow system. However, the physical or chemical conditions, e.g. chemical reactivity, thermal degradation, etc. which exist between the point at which the biocide may be added to the system and the point at which its biocidal effect is desired render the effective use of a biocide impossible.

Similarly, in a system experiencing relatively slow flow, such as a paper mill, if a biocide is added at the beginning of the system, its biocidal effect may be completely dissipated before it has reached all of the points at which this effect is desired or required. As a consequence, the biocide must be added at a plurality of points, and even then a graduated biocidal effect will be experienced between one point of addition to the system and the next point downstream at which the biocides may be added. In addition to the increased cost of utilizing and maintaining plural feed points, gross ineconomies in respect to the cost of the biocide are experienced. Specifically, at each point of addition, an excess of the biocide is added to the system in order to compensate for that portion of the biocide which will be expended in reacting with other constituents present in the system or experience physical changes which impair its biocidal activity.

It is an object of the present invention to provide methods and compositions for controlling slimeforming microorganisms in aqueous systems such as cooling water systems and pulp and paper mill systems, and for controlling slime formation or microorganism populations in aqueous bodies in general. Moreover, another object of the invention is the provision of methods and compositions for controlling slimeforming microorganisms in any aqueous system which is conducive to the growth and reproduction of microorganisms and, in particular, cooling water and paper and pulp mill systems which employ a combination of a bromonitrostyrene and a quaternary ammonium cati- 3 onic compound as the slime control agent, specifically cetyl trimethyl ammonium p-toluene sulfonate and its derivatives.

In the practice of the invention, the combination is EXAMPLE I Synergism was demonstrated by adding Compound A and Compound B in varying ratios and over a range of concentrations to liquid nutrient agar medium (Trypadded to the particular system being treated, for exam- 5 tone Glucose Extract Agar) at approximately 5 coolmg water Systems paper pulp {mu Systems After the medium had solidified in Petri plates, it was pools ponds lagoons k m a qua.nmy adfaquate inoculated with a bacterial suspension. Following two to control the Shme'tjormmg mlcroorgamsm? which are daysincubation, the lowest concentration of each ratio contained or whlch m become entramed the which prevented growth on the agar medium was taken system to be treated n has been found that such as the end point. End points for the various mixtures positions and coritrol the growth and occur' were then compared with end points for the pure active rence of such mlcroorgamsms as may populate these ingredients working alone in concomitantly prepared particular systems. As has been documented, bromoniagar medium plates synergism was determined by the trostyrene, although quite effective as a biocide, has method described by F Ku", p Eisman, H the added advantage of being easily detoxified. Acsylwest'rowicz and L Mayer, APPLIED MICRQB]- cordingly, the present invention seeks to make use of OLOGY 9, 53841, (1946), and the l i hi the biocidal activity, further enhanced by the inclusion of the quaternary compound, with the knowledge that pollutional standards can be complied with. 20 Q Q,, 1 is synergism, 1 is antagonism and Bromonitrostyrene or, more specifically, betabromo- Q Q 18 addmvlty betanitrostyrene (the cis, trans or mixed forms) posh w ere, 23 33112 1 53: 1:; formula C6H5CH=CBrNOz and the Q,, Quantity of Compound A, acting alone, producmg an end pomt 25 Q,,= Quantity of Compound B, acting alone, producing an end point Br Q,, Quantity of Compound A, in the mixture, pro- C6l-15-CH=C ducing an end pomt N 2 Q, Quantity of Compound B, in the mixture, producing an end point For mixtures of Compounds A and B, and for Compound A and Compound 13 acting alone, the following As earlier stated, the inventive composltrons comresults were observed Prise a combination of the betabromo'bem' Summary of synergistic activity of varying percentages nitrostyrene and cetyl trimethyl ammonium p-toluene of the cetyl trimethyl ammonium Holuene lf ate sulfonate, either compound being present in such a compound and b i t quantity as to impart a synergistic behavior to the com- SYNERGISTIC COMBINATION position as a whole, the weight ratio of the styrene to Compound Betabrommbetanitrostyrene the sulfonate ranging from about 10:90 to about 95:5. Compound 3; c l i h l ammonium p-toluene When these two ingredients are mixed, the resulting 40 lf nat TABLE 1 TEST ORGANISM AEROBACTER AEROGENES Weight Ratio Quantities Producing End Points (ppm) Q4 Q8 QL Q Q ofA to B Mixture Q,,

mixtures possess a high degree of slimicidal activity The mode of establishing the synergistic behavior of which could not have been predicted beforehand from the compositions of the present invention is a widely the known activity of the individual ingredients comused and an industrially acceptable procedure. A1- prising the mixture. Accordingly, it is therefore possithough it is believed that the above is sufficient in exble to produce a more effective slime-control agent plaining the procedure,for afurther description therethan has previously been available. Because of the enof reference can be made to US. Pat. No. 3,231,509 hanced activity of the mixture, the total quantity of the and its file history where data of this nature was considbiocide required for an effective treatment may be reered to be acceptable. Moreover, the acticle by Kull et duced. In addition, the high degree of biocidal effeca] published in APPLIED MICROBIOLOGY, 9, tiveness which is provided by each of the ingredients 538-541, will furnish additional information in this remay be exploited without use of the higher concentraga tions of each. For the testing to ascertain synergistic behavior, Aer- To demonstrate the synergism which is provided by the inventive combinations of compounds, the data as set forth in the Table below was developed.

obacter aerogenes was favored since this microorganism is found to exist and found to be most troublesome in pulp and paper producing processes, as well as in cooling towers. Moreover, this microorganism is difficult to control and/or kill and accordingly its existence does give rise to troublesome slime. In view of the foregoing, it can then be appreciated that since Aerobacter aerogenes is prevalent in most slime-affected systems and since this microorganism is difficult to control or kill, that once control of this microorganism is maintained, then for all practical purposes the total microorganism population with its different types is considered controlled.

When the inventive compositions are employed in the treatment of cooling or paper mill water, they are preferably utilized in the form of relatively dilute solutions or dispersions. For example, a preferred solution comprises between 5% to 65% by weight of the synergistic combination in admixture with various solvents and solubilizing agents. An example of such a synergistic composition comprises by weight of bromonitrostyrene, 10% of cetyl trimethyl ammonium ptoluene sulfonate and the remainder composed of such materials as surfactants, organic solvents and/or water.

Surfactants such as the alkylaryl polyether alcohols, polyether alcohols, alkyl benzene sulfonates and sulfates, and the like, may also be employed to enhance the dispersibility and stability of these formulations. The foregoing solutions of the biocidal compositions are utilized in order to insure the rapid and uniform dispersibility of the biocides within the industrial water which is treated. It has been found that either aqueous or non-aqueous solvents are generally suitable in the preparation of compositions of the invention. For example, organic solvents such as methyl cellosolve and aliphatic and aromatic hydrocarbons, e.g. kerosene, can be used quite successfully. Based upon the synergism study as outlined above, it was ascertained that in the treatment of paper mill and cooling water, effective biocidal action is obtained when the concentration or treatment level of the combination or admixture of biocides is between 0.5 parts per million to 1,000 parts per million, and preferably between 1 and 100 parts per million, based upon the total content of the system treated, such as the total quantity of cooling water or paper mill water. 1

The compositions may also be utilized for the preservation of slurries and emulsions containing carbohydrates, proteins, fats, oils, etc. Dosage levels for this purpose range in the vicinity of 0.01% to 5%.

The compositions of the invention which can be prepared by merely combining the respective ingredients and mixing thoroughly at standard conditions may be fed continuously to the treated system, e.g. by means of a metered pump, or may be fed periodically at intervals calculated to control the growth of slime-forming organisms in the system. Naturally, in the treatment of cooling water the feeding of the inventive compositions must be designed to compensate for blowdown in those systems which employ that expedient.

Although the styrene compound has been limited in this description to a specific styrene, it is obvious that slight modifications of this compound would also operate in the same manner. These modifications would be obvious to the worker once apprised of the invention. Accordingly, modifications of this nature are included within the general scope of the invention.

As would be expected, the inventive composition may be added to the cooling water or paper and pulp mill systems at any convenient point. Naturally, in

once-through or non-circulating systems, the composition must be added upstream from the point or points at which microorganism control is desired. In circulating systems or pulp and paper systems, the compositions may be added at any point provided that the time lapse and the conditions experienced between point of addition and the point at which the effect of the composition is experienced are not so drastic as to result in the neutralization of the effect of the composition.

SLIME CONTROL EFFECTIVENESS The inventive methods and materials were tested with respect to their performance in the control of slime formation in industrial systems. In this test an industrial recirculating water was obtained from a system which was currently experiencing problems in respect to the formation of slime by microorganisms. Such tests do not demonstrate the efficiency of the biocide employed with respect to specific species of microorganisms but instead supply a practical demonstration of the efficacy of the biocide tested in relation to those communities of microorganisms which have evidenced their ability to form slime in actual industrial systems.

In testing of recirculating water samples, a substrate evaluation was employed. In such testing, identical portions of water samples are treated with varying concentrations of biocide and two portions are left untreated to serve as controls. The control portions are plated for total count at the beginning of biocide treatment and all portions are plated for total count at some suitable time period (s) after beginning biocide treatment. Using the counts obtained from the platings, the percentage kill (based on the initial control count) may be calculated. In the following example, the water sample was taken from a paper machine headbox sample from a paper mill located in the northeastern United States.

For the purposes of comparison, a composition of this invention was evaluated with two recognized commercial biocides.

In order to ascertain whether in fact the inventive compositions were effective in controlling fungi, evaluations were made following the procedure described by Shema et a1, JOURNAL FOR THE TECHNICAL AS- SOCIATION OF THE PULP AND PAPER INDUS- TRY, 36, 20A-30A, I953. The described procedure generally entails incorporating the biocide under test in a nutrient substrate such as agar, malt, etc. and pouring the resulting medium in a Petri dish and allowing the medium to solidify. A button of fungus inoculum is placed on the surface of the solidified medium and the medium is incubated for a period of 14 days. After the period, the diameter of the colony is measured and compared with the diameter of the button of inoculum originally placed upon the surface. If there is no increase in the diameter, the growth of the fungus is considered to be completely inhibited and the treatment level which effectuates this is considered the inhibitory concentration.

The fungi species utilized as the test microorganism to evaluate the efficacy of the present compositions were Penicillium expansum and Aspergillus niger. The study revealed that the above active composition of this invention inhibited the growth of Penicillium expansum at a treatment level of 200 ppm and the same amount completely inhibited the growth of Aspergillus niger.

Bactericidal Effectiveness The bactericidal effectiveness of a 50/50 mixture of the two components of this invention (10% active) is demonstrated by the following data in which the inhibiting power is shown in comparison with two commercial biocides. Aerobacter aerogenes was employed as the test organism and a substrate technique was utilized. Specifically, the biocidal mixture was added in gradually increasing quantities to nutrient agar media which was then innoculated with Aerobacter aerogenes. The preparation was then incubated for 48 hours. The below values indicate the quantity of biocide required to achieve complete inhibition of the growth of the test organism.

Inhibition quantity Accordingly, since the waters of pulp and paper mills and the water of cooling water systems generally predominately contain bacteria such as Aerobacter aerogenes and some fungi such as Penicillium expansum and Aspergillus niger, it is apparent from the foregoing evaluations and studies that the inventive composition" will effectuate the claimed objective of controlling microorganisms of aqueous systems.

It should be noted that while the preponderance of evidence has been derived from the treatment of samples taken from paper and pulp mill aqueous systems, the compositions and methods of the present invention are broadly applicable to the treatment of aesthetic waters as well as industrial waters such as cooling waters which are plagued by deposits formed by slime-forming organisms, or by the very presence of such organisms.

Having thus described the invention, what is claimed l. A composition of the control of the growth of the microorganism Aerobacter aerogenes in aqueous systems in which said microorganism is found comprising betabromo-beta-nitrostyrene and cetyl trimethyl am monium p-toluene sulfonate, wherein the weight ratio of the styrene to the sulfonate ranges from about 10:90 to about :5 respectively.

2. The composition of claim 1 where said ratio is about 50:50.

3. A method for controlling the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found which comprises contacting said microorganism in said system with a growth-preventing amount of a composition comprising betabromo-betanitrostyrene and cetyl trimethyl ammonium p-toluene sulfonate, wherein the weight ratio of the styrene to the sulfonate ranges from about 10:90 to about 95:5 respectively.

4. The method of claim 3 where said ratio is about 50:50.

5. The method of claim 3 wherein said composition is added to said system in an amount of from about 0.5 to about 1,000 parts by weight of said composition per million parts by weight of said aqueous system.

6. The method of claim 5 where said composition amount is from about 1 to about parts per million of said aqueous system.

7. The method of claim 5 wherein the aqueous system is that of a cooling water system.

8. The method of claim 5 wherein the aqueous system is that of a pulp and paper mill system. 

1. A COMPOSITION OF THE CONTROL OF THE GROWTH OF THE MICROORGANISM AEROBACTER AEROGENES IN AQUEOUS SYSTEMS IN WHICH SAID MICROORGANISM IS FOUND COMPRISING BETABROMO-BETANITROSTYRENE AND CETYL TEIMETHYL AMMONIUM P-TOLUENE SULFONATE, WHEREIN THE WEIGHT RATIO OF THE STYRENE TO THE SULFONATE RANGES FROM ABOUT 10:90 TO ABOUT 95:5 RESPECTIVELY.
 2. The composition of claim 1 where said ratio is about 50:50.
 3. A method for controlling the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found which comprises contacting said microorganism in said system with a growth-preventing amount of a composition comprising betabromo-beta-nitrostyrene and cetyl trimethyl ammonium p-toluene sulfonate, wherein the weight ratio of the styrene to the sulfonate ranges from about 10:90 to about 95:5 respectively.
 4. The method of claim 3 where said ratio is about 50:50.
 5. The method of claim 3 wherein said composition is added to said system in an amount of from about 0.5 to about 1,000 parts by weight of said composition per million parts by weight of said aqueous system.
 6. The method of claim 5 where said composition amount is from about 1 to about 100 parts per million of said aqueous system.
 7. The method of claim 5 wherein the aqueous system is that of a cooling water system.
 8. The method of claim 5 wherein the aqueous system is that of a pulp and paper mill system. 